CN105561863A - Preparation method of sulfonate type gemini surfactant - Google Patents
Preparation method of sulfonate type gemini surfactant Download PDFInfo
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- CN105561863A CN105561863A CN201410551267.XA CN201410551267A CN105561863A CN 105561863 A CN105561863 A CN 105561863A CN 201410551267 A CN201410551267 A CN 201410551267A CN 105561863 A CN105561863 A CN 105561863A
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Abstract
The invention discloses a preparation method of a sulfonate type gemini surfactant. According to the method, alkylphenol, sodium hydroxide and dibromoalkane generate a bisether intermediate under the action of a phase transfer catalyst tetrabutylammonium bromide in a nucleophilic substitution reaction under an ultrasonic condition; the bisether intermediate and chlorosulfonic acid are subjected to a sulfonation reaction with dichloromethane being a solvent under an ice-water bath condition, and then an alkaline solution is added to generate the sulfonate type gemini surfactant. According to the method, the reaction process is accelerated by the cavatition of ultrasonic waves, selectivity of a target product is improved, and therefore the yield of the intermediate is increased to 94.5% at present from 87% achieved through a common method.
Description
Technical field
The invention belongs to field of fine chemical, relate to a kind of preparation method of sulphonate type gemini surfactant.
Background technology
Gemini surface active agent is made up of two hydrophilic groups, two hydrophobic groups and a spacer group.Special structure makes it have many excellent properties, as higher surface-active, more easily forms the very low and excellent wetability etc. of micelle, Krafft point, thus becomes the focus of many research fields.There is application prospect widely.Owing to having disulfonate structure, sulphonate type gemini surfactant is very well water-soluble, and surface-active improves, and detergency ability, dispersibility, resistance to hard water and stability are also greatly improved.
Document (Zhu Sen, Cheng Fa, the gathering character [J] of the .Gemini aqueous solution of anionic surfactant such as Zheng Baojiang. Acta PhySico-Chimica Sinica, 2004,20 (10): 1245-1248.) once under softex kw catalysis, at 90 DEG C, react 2h with nonyl phenol and sodium hydrate aqueous solution and Isosorbide-5-Nitrae-dibromobutane and synthesize bis ether intermediate.Intermediate and chlorosulfonic acid react generation sulphonate type gemini surfactant further.There is certain deficiency in this intermediate reaction, as higher in reaction temperature and intermediate productive rate cannot improve further.
Summary of the invention
The object of this invention is to provide a kind of preparation method of sulphonate type gemini surfactant.Its reaction is simple, and the time is short, and temperature is low, intermediate productive rate is higher.Target product surface is active better.
Realize the technical scheme of the object of the invention:
A preparation method for sulphonate type gemini surfactant, is characterized in that adopting following steps:
1) nucleophilic substitution: under ultrasound condition, generates bis ether intermediate by alkyl phenol and NaOH and two bromoalkanes under the effect of phase transfer catalyst TBAB;
2) sulfonation and salt-forming reaction: under ice-water bath condition take carrene as solvent, bis ether intermediate and chlorosulfonic acid generation sulfonating reaction, then adds alkaline solution, generates sulphonate type gemini surfactant.
Step 1) described in alkyl phenol select nonyl phenol, two bromoalkanes select Isosorbide-5-Nitrae-dibromobutane or 1,6-dibromo-hexane.
Step 1) described in ultrasound condition be ultrasonic power be 250W, the mol ratio of alkyl phenol and two bromoalkanes is 2.02:1, and the mass fraction of NaOH is 20%.
Step 1) described in reaction temperature be 55 ~ 65 DEG C.
Step 1) described in reaction temperature be 65 DEG C.
Step 2) described in alkaline solution be the ethanolic solution of 30wt% triethanolamine.
Step 2) described in the mol ratio of bis ether intermediate and chlorosulfonic acid be 1:2.5.
Compared with prior art, its remarkable advantage is in the present invention:
1, in the reaction of synthetic intermediate, add the ultrasonic wave of certain power, utilize hyperacoustic cavitation accelerated reaction process, improve the selection of target product, thus make intermediate productive rate bring up to existing 94.5% from 87% of commonsense method.2, the formation of bubble of ultrasonic cavitation experience, growth and collapse three phases.Within a few microsecond, bubble collapses suddenly, and produce localized hyperthermia, rate of temperature change is up to 109K/s.The large energy that cavitation effect produces is conducive to opening chemical bond.Ultrasonic by absorption time, cause second-order effect, as emulsification, heating effect etc.Therefore, the reaction temperature of synthetic intermediate is reduced to 65 DEG C by 90 DEG C.
3, the aqueous slkali that salt-forming reaction is used is become the ethanolic solution of triethanolamine from the ethanolic solution of NaOH.A cmc order of magnitude less of the cmc of the Gemini surface active agent of documents of two kinds of obtained Gemini surface active agents, surface-active is higher, and γ
cmclower, illustrate that the capillary ability of the reduction aqueous solution is stronger.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1
Step one: in the 250mL four-hole boiling flask that reflux condensing tube and thermometer are housed, add 2.02mol (22.22g) nonyl phenol and 2.00g TBAB, add the sodium hydrate aqueous solution that 100mL mass fraction is 20% again, mechanical agitation, open ultrasonic cleaning machine, setting power is 250W.Design temperature, when being warming up to 55 DEG C, adds 0.05mol1,4-dibromobutane, continues to be warming up to 65 DEG C, and adopt thin-layer chromatographic analysis to follow the tracks of reaction process during reaction, solvent is V (benzinum): V (ethyl acetate)=15:1.Reaction 1.5h, reaction terminates.Product is divided into two-phase.After system is cooled to room temperature, with ether (50mL × 3) extraction, then uses deionized water (50mL × 3) to wash extract, then spend the night with anhydrous magnesium sulfate drying.Decompress filter, solvent evaporated, obtains bis ether intermediate, and productive rate is 94.5%.
Step 2: with in the 250mL four-hole boiling flask of hydrogen chloride absorption device, add 0.04mol bis ether intermediate, and add 50mL anhydrous methylene chloride as solvent, magnetic agitation.The 2.5mol chlorosulfonic acid being dissolved in 30mL anhydrous methylene chloride is instilled reaction system in lh under ice-water bath condition, and continue reaction 6h, reaction terminates.Be that the ethanolic solution of the triethanolamine of 20% is neutralized to pH=8 with mass fraction, spend the night.Filter, solvent evaporated, obtains crude product, uses 95% ethyl alcohol recrystallization.Synthetic is as shown in structural formula (1).
Embodiment 2
Step one: in the 250mL four-hole boiling flask that reflux condensing tube and thermometer are housed, add 2.02mol (22.22g) nonyl phenol and 2.00g TBAB, add the sodium hydrate aqueous solution that 100mL mass fraction is 20% again, mechanical agitation, open ultrasonic cleaning machine, setting power is 250W.Design temperature, when being warming up to 55 DEG C, adds 0.05mol1,6-dibromo-hexane, continues to be warming up to 65 DEG C, and adopt thin-layer chromatographic analysis to follow the tracks of reaction process during reaction, solvent is V (benzinum): V (ethyl acetate)=15:1.Reaction 1.5h, reaction terminates.Product is divided into two-phase.After system is cooled to room temperature, with ether (50mL × 3) extraction, then uses deionized water (50mL × 3) to wash extract, then spend the night with anhydrous magnesium sulfate drying.Decompress filter, solvent evaporated, obtains bis ether intermediate, and productive rate is 94%.
Step 2: with in the 250mL four-hole boiling flask of hydrogen chloride absorption device, add 0.04mol bis ether intermediate, and add 50mL anhydrous methylene chloride as solvent, magnetic agitation.The 2.5mol chlorosulfonic acid being dissolved in 30mL anhydrous methylene chloride is instilled reaction system in lh under ice-water bath condition, and continue reaction 6h, reaction terminates.Be that the ethanolic solution of the triethanolamine of 20% is neutralized to pH=8 with mass fraction, spend the night.Filter, solvent evaporated, obtains crude product, uses 95% ethyl alcohol recrystallization.Synthetic is as shown in structural formula (2)
Embodiment 3 (effect example)
HLB value can be used for weighing the quality of emulsifier effect.Structure factor method calculates the computing formula of HLB value: the hydrophilic radix of HLB=7+ ∑-∑ oleophylic radix.The group number of the HLB value of hydrophilic radical and lipophilic group is substituted into the HLB value that formula can obtain target product in embodiment one.HLB＝7+9.4×2+1.9×6+1.3×2-34×0.475-2×1.662＝20.326。
Target product in embodiment one and Span80 are carried out composite come emulsification methyl-silicone oil.From related data, making methyl-silicone oil form the stable HLB value needed for O/W type emulsion is 10.5.From calculating, in embodiment one, target product and Span80 mass ratio are 39:61.
Compound emulsifying agent and 340ml water that 20g made is added in large beaker, after emulsifying agent dissolves completely, open high shearing mixing emulsor, slowly add 40g methyl-silicone oil, emulsification 40min, gets proper amount of silicon fat liquor and is placed in centrifuge tube, centrifugal 30min under the condition of 3000r/min, there is no floating oil droplet phenomenon, not stratified.Emulsifier is 5% (mass fraction).The emulsion uniform and smooth prepared, is creamy white.
Two kinds of obtained Gemini surface active agents and cmc, γ of documents product
cmc, c
20be listed in the table below 1.
Two kinds of Gemini surface active agents obtained by table 1 and cmc, γ of documents product
cmc, c
20
As can be seen from Table 1, a cmc order of magnitude less of the cmc of the Gemini surface active agent of documents of two kinds of obtained Gemini surface active agents, surface-active is higher, and γ
cmclower, illustrate that the capillary ability of the reduction aqueous solution is stronger.
Claims (7)
1. a preparation method for sulphonate type gemini surfactant, is characterized in that adopting following steps:
1) nucleophilic substitution: under ultrasound condition, generates bis ether intermediate by alkyl phenol and NaOH and two bromoalkanes under the effect of phase transfer catalyst TBAB;
2) sulfonation and salt-forming reaction: under ice-water bath condition take carrene as solvent, bis ether intermediate and chlorosulfonic acid generation sulfonating reaction, then adds alkaline solution, generates sulphonate type gemini surfactant.
2. the preparation method of sulphonate type gemini surfactant according to claim 1, is characterized in that, step 1) described in alkyl phenol select nonyl phenol, two bromoalkanes select Isosorbide-5-Nitrae-dibromobutane or 1,6-dibromo-hexane.
3. the preparation method of sulphonate type gemini surfactant according to claim 1, it is characterized in that, step 1) described in ultrasound condition be ultrasonic power be 250W, the mol ratio of alkyl phenol and two bromoalkanes is 2.02:1, and the mass fraction of NaOH is 20%.
4. the preparation method of sulphonate type gemini surfactant according to claim 1, is characterized in that, step 1) described in reaction temperature be 55 ~ 65 DEG C.
5. the preparation method of sulphonate type gemini surfactant according to claim 4, is characterized in that, step 1) described in reaction temperature be 65 DEG C.
6. the preparation method of sulphonate type gemini surfactant according to claim 1, is characterized in that, step 2) described in alkaline solution be the ethanolic solution of 30wt% triethanolamine.
7. the preparation method of sulphonate type gemini surfactant according to claim 1, is characterized in that, step 2) described in the mol ratio of bis ether intermediate and chlorosulfonic acid be 1:2.5.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106866473A (en) * | 2017-01-19 | 2017-06-20 | 中国石油化工股份有限公司 | A kind of high-content wax viscous crude wax is brilliant, asphaltene dispersants |
| CN108285781A (en) * | 2018-03-19 | 2018-07-17 | 青岛大学 | A kind of high contents of calcium and magnesium oil reservoir complexed surfactant oil displacement system |
| CN109517591A (en) * | 2018-11-15 | 2019-03-26 | 中国石油化工股份有限公司石油勘探开发研究院 | A kind of high temperature resistant, Low Damage clean fracturing fluid |
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| CN102126972A (en) * | 2011-01-26 | 2011-07-20 | 齐齐哈尔大学 | Polyoxyethylene alkylphenol ether ester cationic gemini surfactant and preparation method thereof |
| JP2013082651A (en) * | 2011-10-07 | 2013-05-09 | Tokyo Univ Of Science | Gemini surfactant and method of demulsifying emulsion |
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Patent Citations (2)
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| CN102126972A (en) * | 2011-01-26 | 2011-07-20 | 齐齐哈尔大学 | Polyoxyethylene alkylphenol ether ester cationic gemini surfactant and preparation method thereof |
| JP2013082651A (en) * | 2011-10-07 | 2013-05-09 | Tokyo Univ Of Science | Gemini surfactant and method of demulsifying emulsion |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106866473A (en) * | 2017-01-19 | 2017-06-20 | 中国石油化工股份有限公司 | A kind of high-content wax viscous crude wax is brilliant, asphaltene dispersants |
| CN108285781A (en) * | 2018-03-19 | 2018-07-17 | 青岛大学 | A kind of high contents of calcium and magnesium oil reservoir complexed surfactant oil displacement system |
| CN108285781B (en) * | 2018-03-19 | 2021-09-24 | 青岛大学 | Composite surfactant oil displacement system for high-calcium-magnesium oil reservoir |
| CN109517591A (en) * | 2018-11-15 | 2019-03-26 | 中国石油化工股份有限公司石油勘探开发研究院 | A kind of high temperature resistant, Low Damage clean fracturing fluid |
| CN109517591B (en) * | 2018-11-15 | 2021-02-02 | 中国石油化工股份有限公司石油勘探开发研究院 | High-temperature-resistant low-damage clean fracturing fluid |
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Application publication date: 20160511 |